CN105460952B - The ZSM-5 molecular sieve material that the preparation method and this method of a kind of ZSM-5 molecular sieve material are prepared - Google Patents
The ZSM-5 molecular sieve material that the preparation method and this method of a kind of ZSM-5 molecular sieve material are prepared Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 166
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 109
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052593 corundum Inorganic materials 0.000 claims description 28
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 23
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 230000008520 organization Effects 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 28
- 238000002425 crystallisation Methods 0.000 description 26
- 230000008025 crystallization Effects 0.000 description 25
- 235000019353 potassium silicate Nutrition 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 238000003756 stirring Methods 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000004846 x-ray emission Methods 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 14
- 238000004220 aggregation Methods 0.000 description 13
- 230000002776 aggregation Effects 0.000 description 13
- 239000002159 nanocrystal Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 206010013786 Dry skin Diseases 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- VNODFDYEKIODIQ-UHFFFAOYSA-N C(CC)Br(CCC)(CCC)CCC Chemical compound C(CC)Br(CCC)(CCC)CCC VNODFDYEKIODIQ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- -1 isopropyl Aluminium Chemical compound 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- ORVGYTXFUWTWDM-UHFFFAOYSA-N silicic acid;sodium Chemical compound [Na].O[Si](O)(O)O ORVGYTXFUWTWDM-UHFFFAOYSA-N 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a kind of preparation method of 5 molecular screen materials of ZSM, silicon source and optional silicon source are first carried out back flow reaction by this method in alkaline environment, primary gel is obtained, structure directing agent and polyethylene glycol are then successively introduced into primary gel, then carry out hydrothermal crystallizing.Present invention also offers a kind of 5 molecular sieves of Hydrogen ZSM and its application and a kind of methanol conversion process.The method provided by the invention for preparing 5 molecular sieves of ZSM can obtain 5 molecular screen materials of ZSM with micro-nano hierarchical organization；Also, the molecular sieve thus prepared carries out ion exchange and is transformed into after hydrogen type molecular sieve as catalyst in use, showing longer service life and higher catalytic activity；It is raw materials used to derive from a wealth of sources and cost is low in addition, the technological process of this method is succinct.
Description
Technical field
The present invention relates to ZSM-5 points that the preparation method and the method for a kind of ZSM-5 molecular sieve material are prepared
Son sieve material, the invention further relates to a kind of Hydrogen ZSM-5 molecular sieve material and its application, the invention further relates to a kind of methanol
Method for transformation.
Background technology
ZSM-5 molecular sieve is a kind of aluminosilicate molecular sieves material with MFI structure, since it has unique duct
Structure, excellent heat endurance and highly acid, are widely used in during oil refining and chemical reaction.
ZSM-5 molecular sieve has 0.5-0.6 nanometers of medium microcellular structure, is very suitable for shape selectivity catalytic reaction, especially
In the reaction of the reaction of methanol conversion, disproportionated reaction (such as toluene disproportionation process) and alkylated reaction (such as alkylation of toluene reaction)
Show good catalytic effect.
But microcellular structure is unfavorable for diffusion of the molecule in ZSM-5 crystal, molecular sieve is caused to be easy to carbon distribution inactivation, shadow
Service life is rung, limits application of the ZSM-5 molecular sieve in catalytic process.In addition, the particle diameter of molecular sieve is also to its catalytic
Can have influences.In general, the crystal that particle diameter is bigger, diffusion path is longer, and carbon distribution is more obvious.
Nanocrystal has the advantages that space scale is small, can effectively overcome disadvantage mentioned above.But nanometer in industrial production
The separated problem of crystal face just before giving birth product, because common filter cloth is difficult separation nanocrystal, obviously can using centrifugation and/or UF membrane
Production cost is caused to be substantially increased.
Make nanocrystal flock together to form micron order aggregation (that is, forming micro-nano hierarchical organization), can both protect
The advantages of staying the advantage of nanocrystal proliferation in reduction, micron order aggregation scale can also being utilized larger, makes product
It is easily isolated.
Therefore, ZSM-5 molecular sieve of the synthesis with micro-nano hierarchical organization becomes one of hot spot of researcher's concern.
CN102001678A discloses a kind of preparation method of middle hole ZSM-5 zeolite microsphere, and this method is first by nanometer two
Silica carries out surface silanization processing, then by it with 4-propyl bromide and water back flow reaction for a period of time after, with isopropyl
Aluminium alcoholates and alkali mixing, then back flow reaction for a period of time, obtains silica-alumina gel again, silica-alumina gel is carried out hydrothermal crystallizing, from water
Solid is isolated in thermal crystallisation mixture, after the solid being collected into is dried and is roasted, it is micro- to obtain mesoporous ZSM-5 zeolite
Ball.
(Microporous and Mesoporous Material, 156 (2012) such as Teng Xue:97-105) report
Prepared using crystal seed revulsion with the mesoporous ZSM-5 molecular sieve aggregation of intergranular.(the Journal of such as Jinjin Zhao
Material Chemistry,19(2009):7614-7616) reporting to be prepared by polymethyl methacrylate (PMMA) has
The ZSM-5 molecular sieve material of micro-nano hierarchical organization.(Chem.Mater., 21 (2009) such as Jia Hua:2344-2348) report
F127 (that is, EO are introduced in hydrolysis reaction106PO70EO106), so as to prepare the ZSM-5 with micro-nano hierarchical organization
Molecular screen material.
But the existing method for preparing the ZSM-5 molecular sieve material with micro-nano hierarchical organization, its preparation process is still
It is so complex, and raw material sources used in certain methods are not wide and cost is higher.
The content of the invention
It is an object of the invention to provide a kind of method for preparing ZSM-5 molecular sieve material, this method can be prepared with micro-
The ZSM-5 molecular sieve material of nano-scale structure, and preparation process is succinct, it is raw materials used to derive from a wealth of sources and cost is not high.
The present inventor has found in the course of the research, when preparing ZSM-5 molecular sieve, first by silicon source and optionally
Silicon source flows back in alkaline environment, obtains primary gel, and structure directing agent is then successively introduced into primary gel and is gathered
Ethylene glycol, then hydrothermal crystallizing is carried out, the ZSM-5 molecular sieve material with micro-nano hierarchical organization can be obtained；Also, thus prepare
Molecular screen material longer use the longevity in use, showing as catalyst after ion exchange is transformed into hydrogen type molecular sieve
Life.The present invention is completed on this basis.
According to the first aspect of the invention, the present invention provides a kind of preparation method of ZSM-5 molecular sieve material, the party
Method comprises the following steps：
(1) a kind of mixture is flowed back, obtains primary gel, the mixture contains silicon source, alkali, water and optional
Silicon source；
(2) the primary gel is mixed with structure directing agent, the silicon source is with SiO2Meter, source of aluminium is with Al2O3Meter,
For the alkali in terms of oxide, silicon source, silicon source, alkali, the molar ratio of structure directing agent and water are 0-10：200：2-8：10-20：
10000-30000；
(3) mixture that step (2) obtains is mixed with polyethylene glycol；
(4) mixture for obtaining step (3) carries out hydrothermal crystallizing；
(5) mixture obtained hydrothermal crystallizing carries out separation of solid and liquid, obtained solid is dried and optionally
Roasting, obtains the ZSM-5 molecular sieve material.
According to the second aspect of the invention, the present invention provides ZSM-5 molecules prepared by a kind of method by the present invention
Sieve material.
According to the third aspect of the present invention, the present invention provides a kind of Hydrogen ZSM-5 molecular sieve material, Hydrogen ZSM-
5 molecular screen materials ZSM-5 molecular sieve material provided by the present invention is formed through ion exchange.
According to the fourth aspect of the present invention, it is anti-as disproportionation the present invention provides the Hydrogen ZSM-5 molecular sieve material
Should, the application of the catalyst of alkylated reaction or the reaction of methanol conversion.
According to the fifth aspect of the present invention, the present invention provides a kind of methanol conversion process, this method to be included in methanol
Under conversion reaction conditions, by methanol and Hydrogen ZSM-5 molecular sieve material provided by the invention.
The preparation method of ZSM-5 molecular sieve material according to the present invention, used raw material sources are extensive and cheap.
Also, preparation in accordance with the present invention, technological process is succinct, on the one hand without carrying out pre-treatment, the opposing party to reaction raw materials
Face, which respectively walks the obtained mixture of reaction and need not be separated, can be directly used for reacting in next step.In addition, make according to the present invention
Separation of solid and liquid can be achieved (as filtered) using the relatively low method of energy consumption in Preparation Method, the mixture that hydrothermal crystallizing obtains.Thus, this
The preparation method cost of the ZSM-5 molecular sieve material of invention is low and easy to implement, suitable for large-scale production.
Importantly, ZSM-5 molecular sieve material prepared by method using the present invention is transformed into hydrogen through ion exchange
After type molecular sieve, as catalyst in use, showing longer service life, while also there is preferable catalytic activity.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is the XRD diffraction spectrograms for ZSM-5 molecular sieve material, wherein, curve A is prepared by embodiment 1 ZSM-5 points
The XRD spectra of son sieve material；Curve B is the XRD spectra purchased from the ZSM-5 molecular sieve of Nankai's catalyst plant.
Fig. 2 is the SEM photograph of ZSM-5 molecular sieve material low range prepared by embodiment 1.
Fig. 3 is the powerful SEM photograph of ZSM-5 molecular sieve material surface prepared by embodiment 1.
Fig. 4 is the powerful SEM photograph of ZSM-5 molecular sieve material surface prepared by embodiment 2.
Fig. 5 is the powerful SEM photograph of ZSM-5 molecular sieve material surface prepared by embodiment 3.
Embodiment
According to the first aspect of the invention, the present invention provides a kind of preparation method of ZSM-5 molecular sieve material, the party
Method comprises the following steps：
(1) a kind of mixture is flowed back, obtains primary gel, the mixture contains silicon source, alkali, water and optional
Silicon source；
(2) the primary gel is mixed with structure directing agent, the silicon source is with SiO2Meter, source of aluminium is with Al2O3Meter,
For the alkali in terms of oxide, silicon source, silicon source, alkali, the molar ratio of structure directing agent and water are 0-10 (being preferably 1-8)：200：2-
8：10-20：10000-30000；
(3) mixture that step (2) obtains is mixed with polyethylene glycol；
(4) mixture for obtaining step (3) carries out hydrothermal crystallizing；
(5) mixture obtained hydrothermal crystallizing carries out separation of solid and liquid, obtained solid is dried and optionally
Roasting, obtains the ZSM-5 molecular sieve material.
In the present invention, term is " optional " to represent inessential, it can be understood as with or without, including or do not include.
The silicon source can be more than one or both of sodium metasilicate, ethyl orthosilicate and white carbon, be preferably silicic acid
Sodium.When using sodium metasilicate as silicon source, preferably using the sodium metasilicate provided in the form of waterglass.
Source of aluminium can be the water-soluble aluminum salt of water-soluble aluminate and/or inorganic acid.Specifically, source of aluminium can be with
It is preferably sodium aluminate more than one or both of sodium aluminate, aluminum nitrate and aluminum sulfate.
The alkali is inorganic base, can be sodium hydroxide and/or potassium hydroxide, is preferably sodium hydroxide.
The structure directing agent can be common structure directing agent in ZSM-5 molecular sieve synthesis field, preferably water-soluble
Property quaternary ammonium salt, more preferably 4-propyl bromide.
The dosage of the polyethylene glycol can make choice according to the composition of the mixture.Preferably, polyethylene glycol with
The weight ratio of water in the mixture is 0.25-4：1.It is highly preferred that the weight of polyethylene glycol and the water in the mixture
Than for 0.25-3：1.Polyethylene glycol plays the role of surfactant, its number-average molecular weight is preferably 200-20000.The present invention
In, number-average molecular weight is measured using gel permeation chromatography.
In step (1), the temperature of the reflux can be 55-85 DEG C.The time of the hydrolysis can be according to the temperature of reflux
Degree makes choice, so as to making aqueous solution be formed subject to primary gel.Usually, the time of the hydrolysis can be that 24-48 is small
When.
In step (2), the mixing generally carries out under room temperature (generally 10-40 DEG C).The time of the mixing with into
Depending on the temperature of row mixing, when generally can be 1-4 small, when being preferably 3-4 small.
In step (3), the mixture be subject to and can obtain step (2) that mixes is uniformly mixed with polyethylene glycol.One
As, the mixing can carry out under room temperature (generally 10-40 DEG C).When the time of the mixing can be 1-4 small, preferably
For 3-4 it is small when.
In step (4), the hydrothermal crystallizing can carry out under the conventional hydrothermal crystallization condition of ZSM-5 molecular sieve, not have
It is particularly limited to.Usually, the hydrothermal crystallizing can carry out at a temperature of 150-200 DEG C.The time of the hydrothermal crystallizing with
Depending on the temperature of hydrothermal crystallizing.Usually, when the time of the hydrothermal crystallizing can be 12-48 small, when being preferably 24-48 small.
The mixture that hydrothermal crystallizing obtains can use conventional separation method to carry out separation of solid and liquid, therein to isolate
Solid.The method according to the invention, separation of solid and liquid is can be achieved using filtering.
The solid that separation of solid and liquid obtains can under normal conditions be dried and optionally roast, so as to obtain described
ZSM-5 molecular sieve material.Specifically, the drying can carry out at a temperature of 80-120 DEG C, and time of the drying can be with
Made choice according to dry temperature, when generally can be 8-12 small.The purpose of the roasting essentially consists in removing molecular sieve and closes
The material in molecular sieve pore passage, such as structure directing agent are remained in during, can be determined whether according to specifically used requirement
Roasted.It is preferred that roasted after the completion of drying.The roasting can carry out at a temperature of 450-600 DEG C, the roasting
The duration of burning can make choice according to the temperature of roasting, when generally can be 2-5 small.The roasting is generally in air gas
Carried out in atmosphere.
According to the second aspect of the invention, the present invention provides ZSM-5 molecules prepared by a kind of method by the present invention
Sieve material.
ZSM-5 molecular sieve material according to the present invention has micro-nano hierarchical organization, is by nanoscale ZSM-5 Crystallizations
Micron order aggregation.
According to the third aspect of the present invention, the present invention provides a kind of Hydrogen ZSM-5 molecular sieve material, Hydrogen ZSM-
The ZSM-5 molecular sieve material that 5 molecular screen materials are prepared by preparation method using the present invention is formed through ion exchange.
ZSM-5 molecular sieve material prepared by method using the present invention is non-Hydrogen, can be by ion exchange by its turn
It is turned into Hydrogen.The present invention is not particularly limited for the method for ion exchange, conventional method can be used to carry out.For example, can
Ammonium exchange is carried out with the ZSM-5 molecular sieve material for preparing the method for the present invention, is transformed into ammonium type ZSM-5 molecular sieve material,
Then roasted, so as to obtain Hydrogen ZSM-5 molecular sieve material.
The ZSM-5 molecular sieve material of the present invention is converted into Hydrogen ZSM-5 molecular sieve material as catalysis through ion exchange
During agent, during such as catalyst as disproportionated reaction, alkylated reaction or the reaction of methanol conversion, the longer use longevity is shown
Life, while also there is higher catalytic activity.
According to the fourth aspect of the present invention, the present invention provides Hydrogen ZSM-5 molecular sieve material provided by the invention work
For the application of the catalyst of disproportionated reaction, alkylated reaction or the reaction of methanol conversion.
The disproportionated reaction such as toluene disproportionation process, the alkylated reaction such as alkylation of toluene are reacted, and the methanol turns
Change the reaction of reaction such as preparing olefin by conversion of methanol, aromatic hydrocarbons and/or gasoline.
Using the hydrogen type molecular sieve material of the present invention as during the catalyst of above-mentioned reaction, reaction can be under normal conditions
Carry out, be not particularly limited.
According to the fifth aspect of the present invention, the present invention provides a kind of methanol conversion process, this method to be included in methanol
Under conversion reaction conditions, by methanol and Hydrogen ZSM-5 molecular sieve material provided by the invention.
The methanol conversion process of the present invention, for the condition of methanol and Hydrogen ZSM-5 molecular sieve material is no special
Do not limit, can be carried out under the conditions of conventional the reaction of methanol conversion.
The present invention will be described in detail with reference to embodiments, but the scope being not intended to limit the present invention.
In following embodiments and comparative example, in the x-ray diffractometer of the model D/max-2600/pc purchased from Rigaku
Upper progress X-ray diffraction analysis (XRD), in the x-ray fluorescence spectrometry instrument of the model ZSX Primus II purchased from Rigaku
Upper progress x-ray fluorescence spectrometry (XRF).
In following embodiments and comparative example, in the scanning electron microscopy of the model Nova Nano SEM450 purchased from FEI
The pattern of the molecular sieve of preparation is observed on mirror (SEM).
In following embodiments and comparative example, using nitrogen adsorption methods, in the model purchased from Micromeritics
Measurement the specific area on the surface analysis instrument of tristarII3020-M.
Embodiment 1-13 is used to illustrate the present invention.
Embodiment 1
Waterglass, sodium aluminate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 75 DEG C
When stream reaction 24 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, room temperature (for 25 DEG C) after
When continuous stirring reaction 4 is small.Wherein, with Al2O3The sodium aluminate of meter, with SiO2The waterglass of meter, with Na2The sodium hydroxide of O meters, four
The molar ratio of propyl group ammonium bromide and water is 5：200：5：15：20000.Then, it is (several to divide equally that polyethylene glycol is added into three-necked flask
Son amount is 2000, and the weight ratio of polyethylene glycol and water is 1：1), when room temperature (for 25 DEG C) stirring 4 is small, uniform colloidal sol is formed.
Obtained colloidal sol is fitted into closed reactor, when 165 DEG C of crystallization 48 are small.The mixture that crystallization is obtained is filtered, will
After obtained solid is washed under room temperature (for 25 DEG C) with deionized water, when 120 DEG C of dryings 8 are small, then in 550 DEG C of roastings
Burn 3 it is small when so that obtain the present invention molecular screen material.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve (such as Fig. 1 institutes
Show, wherein, curve A is ZSM-5 molecular sieve material prepared by embodiment 1, and curve B is ZSM-5 points purchased from Nankai's catalyst plant
Son sieve)；XRF analysis show, the SiO of the molecular screen material2/Al2O3For 48.The pattern of the molecular screen material is seen with SEM
Examine, it is the micron order aggregation (as shown in Figure 2) being made of nanocrystal (as shown in Figure 3) to determine the molecular screen material.Using
The specific surface area that nitrogen adsorption methods measure the molecular screen material is 350m2/g。
Comparative example 1
Waterglass, sodium aluminate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 75 DEG C
When stream reaction 24 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, room temperature (for 25 DEG C) after
When continuous stirring reaction 4 is small.Obtained mixture is fitted into closed reactor, when 165 DEG C of crystallization 48 are small.Crystallization is obtained
Mixture is filtered, after obtained solid is washed under room temperature (for 25 DEG C) with deionized water, in 120 DEG C dry 8
Hour, then when 550 DEG C of roastings 3 are small, so as to obtain molecular screen material.Wherein, with Al2O3The sodium aluminate of meter, with SiO2Meter
Waterglass, with Na2The molar ratio of sodium hydroxide, 4-propyl bromide and water that O is counted is 5：200：5：15：20000.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 45.The pattern of the molecular screen material is observed with XRD, determines the molecular sieve
Material is ZSM-5.Nitrogen adsorption methods are used to measure the specific surface area of the molecular screen material as 320m2/g.With SEM to the molecular sieve
The pattern of material is observed, and determines the ZSM-5 molecular sieve monocrystalline that the molecular screen material is 5-10 microns.
Comparative example 2
Waterglass, sodium aluminate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 75 DEG C
When stream reaction 24 is small.Then, into three-necked flask, (number-average molecular weight 2000, gathers for addition 4-propyl bromide and polyethylene glycol
The weight ratio of ethylene glycol and water is 1：1), room temperature continue stirring reaction 4 it is small when.Wherein, with Al2O3The sodium aluminate of meter, with SiO2
The waterglass of meter, with Na2The molar ratio of sodium hydroxide, 4-propyl bromide and water that O is counted is 5：200：5：15：20000.Will
To mixture be fitted into closed reactor, when 165 DEG C of crystallization 48 are small.The mixture that crystallization is obtained is filtered, will
To solid washed under room temperature (for 25 DEG C) with deionized water after, in 120 DEG C it is dry 8 it is small when, then in 550 DEG C of roastings
3 it is small when, so as to obtain molecular screen material.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 50.The pattern of the molecular screen material is observed with SEM, determines the molecular sieve
Material is staggeredly growth ZSM-5 twins.Nitrogen adsorption methods are used to measure the specific surface area of the molecular screen material as 330m2/g。
Comparative example 3
By waterglass, sodium aluminate, sodium hydroxide, 4-propyl bromide, polyethylene glycol (number-average molecular weight 2000, poly- second
The weight ratio of glycol and water is 1：1) added with deionized water in three-necked flask, it is small that reaction 24 is stirred at reflux at 75 DEG C in oil bath
When.Wherein, with Al2O3The sodium aluminate of meter, with SiO2The waterglass of meter, with Na2Sodium hydroxide, 4-propyl bromide and the water of O meters
Molar ratio be 5：200：5：15：20000.Obtained mixture is fitted into closed reactor, when 165 DEG C of crystallization 48 are small.
The mixture that crystallization is obtained is filtered, after obtained solid is washed under room temperature (for 25 DEG C) with deionized water,
When 120 DEG C of dryings 8 are small, then when 550 DEG C of roastings 3 are small, so as to obtain molecular screen material.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 60.The pattern of the molecular screen material is observed with SEM, determines the molecular sieve
Material is the ZSM-5 monocrystalline of 200-500nm.Nitrogen adsorption methods are used to measure the specific surface area of the molecular screen material as 340m2/g。
Embodiment 2
Waterglass, sodium aluminate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 75 DEG C
When stream reaction 24 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, room temperature (for 25 DEG C) after
When continuous stirring reaction 4 is small.Wherein, with Al2O3The sodium aluminate of meter, with SiO2The waterglass of meter, with Na2The sodium hydroxide of O meters, four
The molar ratio of propyl group ammonium bromide and water is 3：200：5：15：20000.Then, it is (several to divide equally that polyethylene glycol is added into three-necked flask
Son amount is 2000, and the weight ratio of polyethylene glycol and water is 1：1), when room temperature (for 25 DEG C) stirring 4 is small, uniform colloidal sol is formed.
Obtained colloidal sol is fitted into closed reactor, when 165 DEG C of crystallization 48 are small.The mixture that crystallization is obtained is filtered, will
After obtained solid is washed under room temperature (for 25 DEG C) with deionized water, when 120 DEG C of dryings 8 are small, then in 550 DEG C of roastings
Burn 3 it is small when so that obtain the present invention molecular screen material.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 75.The pattern of the molecular screen material is observed with SEM, determines the molecular sieve
Material is the micron order aggregation being made of nanocrystal (as shown in Figure 4).The molecular screen material is measured using nitrogen adsorption methods
Specific surface area be 360m2/g。
Embodiment 3
Waterglass, sodium aluminate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 75 DEG C
When stream reaction 24 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, room temperature (for 25 DEG C) after
When continuous stirring reaction 4 is small.Wherein, with Al2O3The sodium aluminate of meter, with SiO2The waterglass of meter, with Na2The sodium hydroxide of O meters, four
The molar ratio of propyl group ammonium bromide and water is 1.5：200：5：15：20000.Then, polyethylene glycol is added into three-necked flask, and (number is
Molecular weight is 2000, and the weight ratio of polyethylene glycol and water is 1：1), when room temperature (for 25 DEG C) stirring 4 is small, formed uniform molten
Glue.Obtained colloidal sol is fitted into closed reactor, when 165 DEG C of crystallization 48 are small.The mixture that crystallization is obtained is filtered,
After obtained solid is washed under room temperature (for 25 DEG C) with deionized water, when 120 DEG C of dryings 8 are small, then at 550 DEG C
Roast 3 it is small when so that obtain the present invention molecular screen material.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 147.The pattern of the molecular screen material is observed with SEM, determines the molecule
Sieve material is the micron order aggregation being made of nanocrystal (as shown in Figure 5).The molecular sieve material is measured using nitrogen adsorption methods
The specific surface area of material is 372m2/g。
Embodiment 4
Waterglass, sodium aluminate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 75 DEG C
When stream reaction 24 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, under room temperature (for 25 DEG C)
Continue stirring reaction 4 it is small when.Wherein, with Al2O3The sodium aluminate of meter, with SiO2The waterglass of meter, with Na2The sodium hydroxide of O meters,
The molar ratio of 4-propyl bromide and water is 5：200：5：15：20000.Then, polyethylene glycol is added into three-necked flask, and (number is
Molecular weight is 800, and the weight ratio of polyethylene glycol and water is 2.5：1) when, stirring 4 is small under room temperature (for 25 DEG C), formed uniform
Colloidal sol.Obtained colloidal sol is fitted into closed reactor, when 180 DEG C of crystallization 48 are small.The mixture that crystallization is obtained carried out
Filter, after obtained solid is washed under room temperature (for 25 DEG C) with deionized water, when 120 DEG C of dryings 8 are small, Ran Hou
When 550 DEG C of roastings 3 are small, so as to obtain the molecular screen material of the present invention.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 52.The pattern of the molecular screen material is observed with SEM, determines the molecular sieve
Material is the micron order aggregation being made of nanocrystal.Use nitrogen adsorption methods measure the specific surface area of the molecular screen material for
343m2/g。
Embodiment 5
Waterglass, sodium aluminate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 75 DEG C
When stream reaction 24 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, room temperature (for 25 DEG C) after
When continuous stirring reaction 4 is small.Wherein, with Al2O3The sodium aluminate of meter, with SiO2The waterglass of meter, with Na2The sodium hydroxide of O meters, four
The molar ratio of propyl group ammonium bromide and water is 5：200：5：15：20000.Then, it is (several to divide equally that polyethylene glycol is added into three-necked flask
Son amount is 800, and the weight ratio of polyethylene glycol and water is 0.5：1), when room temperature (for 25 DEG C) stirring 4 is small, formed uniform molten
Glue.Obtained colloidal sol is fitted into closed reactor, when 180 DEG C of crystallization 48 are small.The mixture that crystallization is obtained is filtered,
After obtained solid is washed under room temperature (for 25 DEG C) with deionized water, when 120 DEG C of dryings 10 are small, then 550
DEG C roasting 3 it is small when so that obtain the present invention molecular screen material.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 47.The pattern of the molecular screen material is observed with SEM, determines the molecular sieve
Material is the micron order aggregation being made of nanocrystal.Use nitrogen adsorption methods measure the specific surface area of the molecular screen material for
357m2/g。
Embodiment 6
Waterglass, sodium aluminate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 75 DEG C
When stream reaction 24 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, room temperature (for 25 DEG C) after
When continuous stirring reaction 4 is small.Wherein, with Al2O3The sodium aluminate of meter, with SiO2The waterglass of meter, with Na2The sodium hydroxide of O meters, four
The molar ratio of propyl group ammonium bromide and water is 5：200：5：15：20000.Then, it is (several to divide equally that polyethylene glycol is added into three-necked flask
Son amount is 20000, and the weight ratio of polyethylene glycol and water is 0.25：1), when room temperature (for 25 DEG C) stirring 4 is small, formed uniform
Colloidal sol.Obtained colloidal sol is fitted into closed reactor, when 180 DEG C of crystallization 48 are small.The mixture that crystallization is obtained carried out
Filter, after obtained solid is washed under room temperature (for 25 DEG C) with deionized water, when 120 DEG C of dryings 12 are small, Ran Hou
When 550 DEG C of roastings 3 are small, so as to obtain the molecular screen material of the present invention.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 47.The pattern of the molecular screen material is observed with SEM, determines the molecular sieve
Material is the micron order aggregation being made of nanocrystal.Use nitrogen adsorption methods measure the specific surface area of the molecular screen material for
362m2/g。
Embodiment 7
Waterglass, sodium aluminate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 75 DEG C
When stream reaction 24 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, room temperature (for 25 DEG C) after
When continuous stirring reaction 4 is small.Wherein, with Al2O3The sodium aluminate of meter, with SiO2The waterglass of meter, with Na2The sodium hydroxide of O meters, four
The molar ratio of propyl group ammonium bromide and water is 7：200：5：15：20000.Then, it is (several to divide equally that polyethylene glycol is added into three-necked flask
Son amount is 200, and the weight ratio of polyethylene glycol and water is 0.25：1), when room temperature (for 25 DEG C) stirring 4 is small, formed uniform molten
Glue.Obtained colloidal sol is fitted into closed reactor, when 180 DEG C of crystallization 48 are small.The mixture that crystallization is obtained is filtered,
After obtained solid is washed under room temperature (for 25 DEG C) with deionized water, when 120 DEG C of dryings 10 are small, then 550
DEG C roasting 3 it is small when so that obtain the present invention molecular screen material.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 35.The pattern of the molecular screen material is observed with SEM, determines the molecular sieve
Material is the micron order aggregation being made of nanocrystal.Use nitrogen adsorption methods measure the specific surface area of the molecular screen material for
378m2/g。
Embodiment 8
Waterglass, aluminum nitrate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 85 DEG C
When stream reaction 30 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, room temperature (for 25 DEG C) after
When continuous stirring 3 is small.Wherein, with Al2O3The aluminum nitrate of meter, with SiO2The waterglass of meter, with Na2Sodium hydroxide, the tetrapropyl of O meters
The molar ratio of ammonium bromide and water is 5：200：8：20：15000.Then, polyethylene glycol (number-average molecular weight is added into three-necked flask
For 800, the weight ratio of polyethylene glycol and water is 3：1), when room temperature (for 25 DEG C) stirring 4 is small, uniform colloidal sol is formed.Will
To colloidal sol be fitted into closed reactor, when 200 DEG C of crystallization 24 are small.The mixture that crystallization is obtained is filtered, and will be obtained
Solid washed under room temperature (for 25 DEG C) with deionized water after, in 120 DEG C it is dry 10 it is small when, then roast 3 at 550 DEG C
Hour, so as to obtain the molecular screen material of the present invention.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 70.The pattern of the molecular screen material is observed with SEM, determines the molecular sieve
Material is the micron order aggregation being made of nanocrystal.Use nitrogen adsorption methods measure the specific surface area of the molecular screen material for
328m2/g。
Embodiment 9
Waterglass, aluminum sulfate, sodium hydroxide and deionized water are added in three-necked flask, stirred back in oil bath at 60 DEG C
When stream reaction 48 is small.Then, 4-propyl bromide is added into three-necked flask as structure directing agent, room temperature (for 25 DEG C) after
When continuous stirring reaction 4 is small.With Al2O3The aluminum sulfate of meter, with SiO2The waterglass of meter, with Na2Sodium hydroxide, the tetrapropyl bromine of O meters
The molar ratio for changing ammonium and water is 2：200：3：10：25000.Then, polyethylene glycol is added into three-necked flask (number-average molecular weight is
10000, the weight ratio of polyethylene glycol and water is 0.5：1), when room temperature (for 25 DEG C) stirring 3 is small, uniform colloidal sol is formed.Will
Obtained colloidal sol is fitted into closed reactor, when 160 DEG C of crystallization 24 are small.The mixture that crystallization is obtained is filtered, will
To solid washed under room temperature (for 25 DEG C) with deionized water after, in 120 DEG C it is dry 10 it is small when, then in 550 DEG C of roastings
Burn 3 it is small when so that obtain the present invention molecular screen material.
Obtained molecular screen material is subjected to XRD analysis, it was demonstrated that the molecular screen material is ZSM-5 molecular sieve；XRF analysis table
It is bright, the SiO of the molecular screen material2/Al2O3For 80.The pattern of the molecular screen material is observed with SEM, determines the molecular sieve
Material is the micron order aggregation being made of nanocrystal.Use nitrogen adsorption methods measure the specific surface area of the molecular screen material for
310m2/g。
Embodiment 1-9's as a result, it was confirmed that preparation method of ZSM-5 molecular sieve material using the present invention can be prepared has
The ZSM-5 molecular sieve material of micro-nano hierarchical organization.
Embodiment 10
(1) the sieve sample NH for synthesizing embodiment 14NO3Ion exchange is carried out, is converted into ammonium type ZSM-5 molecular sieve
Material, then when 450 DEG C of roastings 3 are small, so as to obtain the Hydrogen ZSM-5 molecular sieve material of the present invention.
(2) Hydrogen ZSM-5 molecular sieve material prepared by step (1) is put into fixed bed reactors, forms catalyst bed
Layer.Material benzenemethanol is entered to preheating furnace after flow measurement pumps under the carrying as the nitrogen of carrier gas, and in preheating furnace
Gas is vaporized into, subsequently into being reacted in fixed bed reactors.Wherein, the volume ratio of methanol and nitrogen is 1：1, methanol
Weight space velocity is 1.7h-1, temperature is 460 DEG C, and pressure is 0.1MPa (in terms of gauge pressure).
Analyzed from the reaction product of fixed bed reactors output using on-line gas chromatography, calculate dimethyl ether
(DME) selectivity, is as a result listed in table 1.Wherein, dimethyl ether is the mark of catalyst inactivation, and dimethyl ether is selective
Raising show that methanol dehydration is less able.
Comparative example 4
The reaction of methanol conversion is carried out using the method identical with 10 step of embodiment (2), unlike, using purchased from Nankai
The ZSM-5 molecular sieve of catalyst plant, the SiO of the molecular screen material2/Al2O3For 46, the grain size of the ZSM-5 molecular sieve is 2-
3μm.Nitrogen adsorption methods are used to measure the specific surface area of the molecular screen material as 342m2/g。
Analyzed from the reaction product of fixed bed reactors output using on-line gas chromatography, calculate dimethyl ether
(DME) selectivity, is as a result listed in table 1.
Table 1
From the results shown in Table 1, Hydrogen ZSM-5 molecular sieve material according to the present invention is in effect the reaction of methanol conversion
Catalyst when, reaction continue 76 it is small when after, very low level is remained within to the selectivity of DME, shows catalyst still
It is so active, thus there is longer service life.
Embodiment 11
The ZSM-5 molecular sieve material for being prepared embodiment 2 using the method identical with 10 step of embodiment (1) carries out ion
Exchange is converted into Hydrogen ZSM-5 molecular sieve material, then carries out methanol conversion using the method identical with 10 step of embodiment (2)
Reaction.
Analyzed from the reaction product of fixed bed reactors output using on-line gas chromatography, calculate dimethyl ether
(DME) selectivity, is as a result listed in table 2.
Table 2
Embodiment 12
The ZSM-5 molecular sieve material for being prepared embodiment 3 using the method identical with 10 step of embodiment (1) carries out ion
Exchange is converted into Hydrogen ZSM-5 molecular sieve material, then carries out methanol conversion using the method identical with 10 step of embodiment (2)
Reaction.
Analyzed from the reaction product of fixed bed reactors output using on-line gas chromatography, calculate dimethyl ether
(DME) selectivity, is as a result listed in table 3.
Table 3
Embodiment 13
The ZSM-5 molecular sieve material for being prepared embodiment 4 using the method identical with 10 step of embodiment (1) carries out ion
Exchange is converted into Hydrogen ZSM-5 molecular sieve material, then carries out methanol conversion using the method identical with 10 step of embodiment (2)
Reaction.
Analyzed from the reaction product of fixed bed reactors output using on-line gas chromatography, calculate dimethyl ether
(DME) selectivity, is as a result listed in table 4.
Table 4
The result of embodiment 11-13 also confirms that Hydrogen ZSM-5 molecular sieve material according to the present invention is in effect methanol conversion
During the catalyst of reaction, very low level can will be maintained to the selectivity of DME in longer time, thus with longer
Service life.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of preparation method of ZSM-5 molecular sieve material, this method comprise the following steps：
(1) a kind of mixture is flowed back, obtains primary gel, the mixture contains silicon source, alkali, water and silicon source；
(2) the primary gel is mixed with structure directing agent, the silicon source is with SiO2Meter, source of aluminium is with Al2O3Meter, it is described
For alkali in terms of oxide, silicon source, silicon source, alkali, the molar ratio of structure directing agent and water are 1-10：200：2-8：10-20：10000-
30000；
(3) mixture that step (2) obtains is mixed with polyethylene glycol；
(4) mixture for obtaining step (3) carries out hydrothermal crystallizing；
(5) mixture for obtaining hydrothermal crystallizing carries out separation of solid and liquid, and obtained solid is dried and is optionally roasted,
Obtain the ZSM-5 molecular sieve material.
2. according to the method described in claim 1, wherein, the weight of polyethylene glycol described in step (3) and water described in step (1)
It is 0.25-4 to measure ratio：1.
3. method according to claim 1 or 2, wherein, in step (3), the mixing carries out at room temperature, the mixing
Time for 1-4 it is small when.
4. according to the method described in claim 1, wherein, the silicon source is one in sodium metasilicate, ethyl orthosilicate and white carbon
Kind is two or more；
Source of aluminium is more than one or both of sodium aluminate, aluminum nitrate and aluminum sulfate.
5. the method according to claim 1 or 4, wherein, the alkali is sodium hydroxide and/or potassium hydroxide.
6. the method according to claim 1 or 4, wherein, the structure directing agent is soluble quaternary ammonium.
7. according to the method described in claim 6, wherein, the structure directing agent is 4-propyl bromide.
8. the method according to claim 1 or 4, wherein, in step (1), the temperature of the reflux is 55-85 DEG C, described
When the time of reflux is 24-48 small.
9. according to the method described in claim 1, wherein, in step (2), the mixing carries out at room temperature, the mixing
When time is 1-4 small.
10. according to the method described in claim 1, wherein, in step (4), the hydrothermal crystallizing is at a temperature of 150-200 DEG C
Carry out, when the time of the hydrothermal crystallizing is 12-48 small.
11. according to the method described in claim 1, wherein, the drying carries out at a temperature of 80-120 DEG C, the roasting exists
Carried out at a temperature of 450-600 DEG C.
12. the ZSM-5 molecular sieve material prepared as the method described in any one in claim 1-11.
13. a kind of Hydrogen ZSM-5 molecular sieve material, the Hydrogen ZSM-5 molecular sieve material is as the ZSM-5 described in claim 12 points
Son sieve material is formed through ion exchange.
14. the Hydrogen ZSM-5 molecular sieve material described in claim 13 is converted as disproportionated reaction, alkylated reaction or methanol
The application of the catalyst of reaction.
15. a kind of methanol conversion process, this method are included under the conditions of the reaction of methanol conversion, by described in methanol and claim 13
Hydrogen ZSM-5 molecular sieve material.
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| KR100232333B1 (en) * | 1991-10-23 | 1999-12-01 | 로버트 노르토버 | Nanometer-sized molecular sieve crystals or agglomerates and processes for their production |
| JP4680515B2 (en) * | 2004-02-10 | 2011-05-11 | 東ソー株式会社 | Nanocrystalline zeolite particles and production method thereof |
| CN100368294C (en) * | 2005-08-15 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain |
| US20110117007A1 (en) * | 2009-11-13 | 2011-05-19 | Chervon U.S.A. Inc. | Method for making mfi-type molecular sieves |
| US8951498B2 (en) * | 2010-07-30 | 2015-02-10 | University Of Iowa Research Foundation | Synthesis of hierarchical nanocrystalline zeolites with controlled particle size and mesoporosity |
| CN102001678B (en) * | 2010-10-30 | 2012-03-28 | 太原理工大学 | Middle hole ZSM-5 zeolite microsphere and preparation method thereof |
| CN102963907A (en) * | 2012-12-03 | 2013-03-13 | 华东师范大学 | Pentasil type zeolite molecular sieve synthetic method |
| CN103626203B (en) * | 2013-10-24 | 2018-02-09 | 碗海鹰 | A kind of preparation of nanometer of molecular sieve of ZSM 5 |
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